JP2949525B2 - Polyamide resin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel polyamide resin.

[0002]

2. Description of the Related Art Polyamide resins are widely used as engineering plastics, synthetic fibers, heat-resistant adhesives, etc. because of their excellent heat resistance, impact resistance, solvent resistance, toughness and the like.

However, the conventionally proposed polyamide resin has excellent mechanical properties and heat resistance, but has poor processability and compatibility with other resins due to low solvent solubility, and its use is limited. In addition, since it has a problem of high hygroscopicity, it is difficult to apply it particularly to the field of electronic materials.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and has a low hygroscopicity, a high solvent solubility, a high processability, and a high compatibility with other resins. Accordingly, it is an object of the present invention to provide a novel polyamide resin having utility as a resin modifier.

[0005]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above-mentioned problems in the prior art, and as a result, a polyamide resin was obtained by polycondensation of a diamine compound and an aromatic dicarboxylic acid. It has been found that the above problem can be solved by including a repeating unit having a specific structure in the main chain during production, and the present invention has been completed.

That is, the polyamide resin of the present invention has the following general formula [I]

Embedded image (Wherein, R is lower alkyl optionally substituted phenyl group with a group, R ¹ is carbon atoms showed 1-22 alkyl group, m and n, 1> m / (m + n) ≧ 0. (An integer that satisfies 2), characterized in that the repeating units are randomly bonded by an -NHCO- bond and have an intrinsic viscosity of 0.1 to 3.0 dl / g.
In this specification, the intrinsic viscosity is defined as a resin concentration of 0.5
It means the measured value of g / dl dimethylacetamide solution at 30 ° C.

The present invention contains the repeating unit represented by the above general formula [I] and has an intrinsic viscosity of 0.1 to 3.0 dl /.
The polyamide resin in the range of g can be produced by a polycondensation reaction between a diamine and a dicarboxylic acid. That is, an aromatic diamine H ₂ N—R—NH ₂ [II] represented by the following general formula [II] (wherein R represents a phenyl group which may be substituted by a lower alkyl group) and the following general formula [III Aromatic dicarboxylic acid represented by

[0009]

[0010]

Embedded image Once to synthesize a hydroxyl-containing polyamide resin having a repeating unit represented by the following general formula (IV) by a polycondensation reaction,

[0011]

Embedded image (Wherein, R represents a phenyl group which may be substituted with a lower alkyl group.) Accordingly After the general formula by addition of the alkyl compound as described below to hydroxyl moieties of the hydroxyl group-containing polyamide resin [I The polyamide represented by
Resin can be manufactured.

The aromatic diamine represented by the general formula [II] used in the synthesis of the polyamide resin of the present invention includes, for example, m-phenylenediamine, p-phenylenediamine, metatolylenediamine, 4,4'- Diaminodiphenyl ether, 3,3′-dimethyl-4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether,
4,4'-diaminodiphenylthioether, 3,3 '
-Dimethyl-4,4'-diaminodiphenylthioether, 3,3'-diethoxy-4,4'-diaminodiphenylthioether, 3,3'-diaminodiphenylthioether, 4,4'-diaminobenzophenone, 3,
3′-dimethyl-4,4′-diaminobenzophenone,
3,3′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 3,3′-dimethoxy-4,
4'-diaminodiphenylmethane, 2,2'-bis (3
-Aminophenyl) propane, 2,2'-bis (4-aminophenyl) propane, 4,4'-diaminodiphenylsulfoxide, 4,4'-diaminodiphenylsulfone, benzidine, 3,3'-dimethylbenzidine, ,
There are 3′-dimethoxybenzidine, 3,3′-diaminobiphenyl, p-xylylenediamine, m-xylylenediamine, 3,3-diaminobenzophenone and the like, which can be used alone or in combination.

[0013]

[0014] On the other hand, the general formula for use in preparing the polyamide resin shown by the general formula [I] of the present invention [II
Examples of the hydroxyl-containing aromatic dicarboxylic acid represented by I] include 3-hydroxyphthalic acid, 4-hydroxyphthalic acid, 2-hydroxyphthalic acid, 4-hydroxyisophthalic acid, 5-hydroxyisophthalic acid, and 2-hydroxyterephthalic acid , 3-hydroxyterephthalic acid, and the like.

There are various known methods for synthesizing the above general formula [IV] by polycondensing the above diamine and dicarboxylic acid, but polycondensation using a phosphite condensing agent and a pyridine derivative is known. Reaction is preferred. This is advantageous not only in that a polycondensation reaction can be caused at a relatively low temperature, but also in that a side reaction with the hydroxyl group of the hydroxyl group-containing dicarboxylic acid hardly occurs. Examples of the phosphite-based condensing agent include triphenyl phosphite, diphenyl phosphite, tri-o-tolyl phosphite, and di-o-phosphite.
Tolyl, tri-m-tolyl phosphite, di-m-phosphite
Tolyl, tri-p-tolyl phosphite, di-p-phosphite
Tolyl, di-o-chlorophenyl phosphite, tri-p-chlorophenyl phosphite, di-p-chlorophenyl phosphite and the like can be mentioned. Further, as the pyridine derivative used together with the phosphite in the present invention, pyridine, 2-picoline, 3-picoline, 4-picoline, 2,4-lutidine, 2,5-lutidine, 3,5-
Lutidine and the like can be mentioned.

In conducting the polycondensation reaction in the above reaction in the presence of a phosphite and a pyridine derivative, a solution polymerization method using a mixed solvent containing the pyridine derivative is employed. In the present invention, the organic solvent used is limited in that it does not substantially react with both the reaction components and the phosphite, but in addition, it is desirable that the organic solvent be a good solvent for both the reaction components. Representative examples of such organic solvents are amide solvents such as N-methyl-2-pyrrolidone and dimethylacetamide. In order to obtain a polymer having a high degree of polymerization in the present invention, inorganic salts such as lithium chloride and calcium chloride can be added to this reaction system.

The method for synthesizing a polyamide resin having a repeating unit represented by the above general formula [I] or [IV] will be described in more detail. The synthesis reaction comprises the reaction of the aromatic diamine and aromatic dicarboxylic acid with It can be easily carried out by heating and stirring in an organic solvent such as N-methyl-2-pyrrolidone under an inert atmosphere such as nitrogen in the presence of a phosphite and a pyridine derivative. The amount of the phosphite-based condensing agent used in the polycondensation is at least equimolar to the carboxyl group, but the use of more than 30 times the molar amount is not economically preferable. Further, the amount of the pyridine derivative used in the present invention is required to be at least equimolar to the carboxyl group,
In practice, it is often used in a large excess, including its role as a reaction solvent. As the reaction solvent, a pyridine derivative and N
-Methyl-2-pyrrolidone is preferably used.
An amount of about 30% by weight is used. The reaction temperature is 6
A range from 0 to 140C is preferred. The reaction time is greatly affected by the reaction temperature, but in any case it is advisable to stir the reaction system until the highest viscosity, which means the highest degree of polymerization, is obtained, often between a few minutes and 20 hours.

After completion of the synthesis reaction, the reaction mixture is poured into a non-solvent such as methanol or hexane to separate the produced polymer, and further purified by a reprecipitation method to remove by-products and inorganic salts. yo is, it is possible to obtain an intermediate product represented by the previous following general formula [IV].

The thus obtained general formula [IV]
As a method for converting a hydroxyl group-containing polyamide having a repeating unit represented by the formula into the polyamide resin of the present invention represented by the general formula [I] by a polymer reaction, the above-mentioned general formula [IV] and an alkali metal or a hydroxide thereof alkyl iodide, an alkyl bromide in the presence of such an object, alkyl reaction with alkyl chloride and the like, reaction with dialkyl sulfate in an alkaline solution of the above general formula [IV], the general formula [IV]
And p -toluenesulfonic acid alkyl ester,
Or, dehydration reaction with an alkyl alcohol with an acid catalyst under the above general formula [IV], further, there is a reaction, etc. Various known methods of the above general formula [IV] with alkyl-onium salts, but these are in the present invention It is not limited.

As a method for synthesizing the polyamide resin having the repeating unit represented by the above general formula [I] of the present invention, the alkyl halide, dialkyl sulfate and alkyl P-toluenesulfonate of the above-mentioned production method 2 are used. The alkylation method described above is preferred because of the ease of synthesis and many of these alkyl compounds, which are easily available as commercial products and are advantageous in terms of cost.

The content of the repeating unit of the above general formula [I] constituting the polyamide resin of the present invention is 20 mol% with respect to all the repeating units in order to sufficiently reflect the effect of introducing an alkyl group on the properties. That is all.

[0022]

EXAMPLE 1 16.2 g of m-phenylenediamine (1
50 mmol), 5-hydroxyisophthalic acid 27.0
g (150 mmol), 250 ml of pyridine, 62 g (200 mmol) of triphenyl phosphite, and 10.6 g (250 mmol) of lithium chloride were stirred at 100 ° C. for 4 hours. After standing to cool, the mixed solution was added to methanol 3
000 ml, and the mixture was stirred at room temperature for 1 hour. The precipitated solid was separated by filtration and dried to obtain a hydroxyl group-containing polyamide resin.

After dissolving 10 g of the hydroxyl-containing polyamide resin in 200 ml of dimethylacetamide under a nitrogen atmosphere,
0.90 g (39 mmol) of metallic sodium, di (n-
After 41 g (39 mmol) of butyl) sulfuric acid was added dropwise over 1 hour and reacted at room temperature for 1 hour, the mixture was further reacted at 100 ° C. with stirring for 8 hours. This solution was added dropwise to a large amount of methanol to precipitate a polymer. After filtration, the polymer was washed three times with a large amount of methanol, hexane, and ether, dried at 100 ° C. overnight under vacuum, and subjected to the formula in Table 1. A polyamide resin of the present invention containing the repeating unit shown in (1) was obtained.

Example 2 A hydroxyl group-containing polyamide resin was synthesized in exactly the same manner as in Example 1 except that m-phenylenediamine was replaced with 30 g (150 mmol) of 3,4'-diaminodiphenyl ether. After dissolving 10 g of the resin in 200 ml of dimethylacetamide under a nitrogen atmosphere, the resin was further dissolved in 0.1 ml of sodium metal.
67 g (29 mmol) was dissolved, and 5.8 g (29 mmol) of p-toluenesulfonic acid methyl ester was added dropwise at room temperature over 1 hour.
The reaction was performed for 0 hours. This solution was dropped into a large amount of methanol to precipitate a polymer, and the polymer was separated by filtration in the same manner as in Example 1.
After washing and drying, a polyamide resin of the present invention containing a repeating unit represented by the formula (2) in Table 1 was obtained.

Example 3 A hydroxyl group-containing polyamide resin was synthesized in exactly the same manner as in Example 1 except that m-phenylenediamine was replaced by 31.8 g (150 mmol) of 3,3-diaminobenzophenone. After dissolving 10 g of the resin in 200 ml of dimethylacetamide under a nitrogen atmosphere, 0.64
g (28 mmol) was dissolved, 4.6 g (28 mmol) of n-hexyl bromide was added dropwise, and the mixture was heated to 100 ° C.
The reaction was carried out for 14 hours with stirring. After completion of the reaction, the solution was dropped into a large amount of methanol to precipitate a polymer, which was separated by filtration, washed and dried to obtain a polyamide resin of the present invention containing a repeating unit shown in the formula (3) in Table 1. .

Example 4 The m-phenylenediamine of Example 1 was mixed with 30 g (150 mmol) of 3,4'-oxydianiline and 27.0 g (150 mmol) of 5-bidroxyisophthalic acid.
3.5 g (75 mmol) were replaced and isophthalic acid 1
A hydroxyl group-containing polyamide resin was synthesized in exactly the same manner except that 2.3 g (75 mmol) was added.

After dissolving 10 g of the above polyamide resin in 200 ml of dimethylacetamide under a nitrogen atmosphere,
0.40 g (17 mmol) of sodium metal and 4.8 g (17 mmol) of p-toluenesulfonic acid n-octyl ester were added, and an alkylation reaction was carried out in exactly the same manner as in Example 1; The polyamide resin of the present invention having the repeating unit shown in 4) was obtained.

Example 5 In Example 1, 41 g of di (n-butyl) sulfuric acid (39 g) was used.
Mmol) was replaced by 8.6 g (39 mmol) of n-decyl bromide in exactly the same manner as in formula (5) in Table 1.
The polyamide resin of the present invention represented by the following formula was obtained.

[0029] In Example 6 Example 2, p - toluenesulfonic acid methyl ester 5.8g (29 mmol), p-toluenesulfonic acid n- octadecyl ester 12.3g exactly the same except that instead of (29 mmol) By the method, a polyamide resin of the present invention having a repeating unit represented by the formula (6) in Table 1 was obtained.

Example 7 In Example 3, 4.6 g of n-hexyl bromide was used.
(28 mmol) was replaced with 11.9 g (28 mmol) of p-toluenesulfonic acid n-octadecyl ester, and the polyamide resin of the present invention having a repeating unit represented by the formula (7) in Table 1 in exactly the same manner. I got

Example 8 In Example 1, 41 g of di (n-butyl) sulfuric acid (39 g) was used.
Mmol) was replaced with 16.5 g (39 mmol) of p-toluenesulfonic acid n-octadecyl ester to obtain the polyamide resin of the present invention having a repeating unit represented by the formula (8) in Table 1 in exactly the same manner. Was.

The intrinsic viscosity (measured at 30 ° C. in a 0.5 g / dl dimethylacetamide solution) of the polyamide resin of the present invention obtained in Examples 1 to 8 was measured. Further, the infrared absorption spectrum of the polyamide resin was measured by FX6160 manufactured by Analect Co., Ltd., and -NHC (=
0) - of C = 0 corresponding to 1659～1665Cm ^-1 and 2799～2805Cm ^-1 corresponding to terminal methyl group
And the absorption was confirmed, and it was confirmed that it was the polyamide resin of the present invention.

The results of elemental analysis of the polyamide resin (Carlo Elver 1108 type) and H ¹ -NMR in deuterated dimethyl sulfoxide (PJ manufactured by JEOL Ltd.)
SX60SI), the addition ratio of the substituted alkyl group (R ¹ ) determined from the results of the integral value of the aromatic ring hydrogen and the amide bond hydrogen and the integral value of the alkyl group hydrogen, etc., measured using the repeating unit of each polyamide resin. Are shown in Table 1.

[0034]

[Table 1]

[0035]

The polyamide resin containing an alkyl group of the present invention not only has excellent solvent solubility and compatibility with other resins without impairing properties such as heat resistance and toughness, but also contains an alkyl group. As a result, the hygroscopicity is low, so that application to a wide range can be expected.

Claims (1)

(57) [Claims] [Claim 1] The following general formula (1) (Wherein, R is lower alkyl optionally substituted phenyl group with a group, R ¹ is carbon atoms showed 1-22 alkyl group, m and n, 1> m / (m + n) ≧ 0. A polyamide resin comprising a repeating unit represented by the formula (2), wherein the repeating unit is randomly bonded by an -NHCO- bond, and has an intrinsic viscosity of 0.1 to 3.0 dl / g.